Built detergent compositions containing dextrin esters of poly carboxylic acids

ABSTRACT

Detergent compositions comprising a combination of certain water-soluble organic surface-active agents and, as detergent builders, certain water-soluble salts of dextrin polycarboxylates.

AU 165 EX 0 R 3 9 9 l 9 9 1 0 7 United States Patent 1191 Thompson 1BUILT DETERGENT COMPOSITIONS CONTAINING DEXTRIN ESTERS OF POLYCARBOXYLIC ACIDS [75] Inventor: James Edwin Thompson, Cincinnati.

Ohio

[73] Assignee: The Procter & Gamble Company, Cincinnati, Ohio [22.1Filed: Mar. 23, 1973 1211 Appl. No.: 344,465

[52] US. Cl. 252/99; 252/89; 252/132; 252/135; 252/180; 252/532;252/536; 252/551; 252/555; 260/233.5

1511 1111.01. c111) 1/08 [58] Field of Search 252/135, 95. 99

[56] References Cited UNITED STATES PATENTS 2.311.008 2/1943 Tucker252/89 X 3.332.880 7/1967 Kessler et al. 252/161 3.494.786 2/1971)Nielsen 252/95 Prinmry Eruminer-Benjamin R. Padgett AssistantErnminer-Christine M. Nucker Attorney, Agent, or Firm-George W. Allen;Jerry .1. Yetter; Jack D. Schaeffer [57] ABSTRACT Detergent compositionscomprising a combination of certain water-soluble organic surface-activeagents and, as detergent builders, certain water-soluble salts ofdextrin polycarboxylates.

10 Claims, No Drawings BUILT DETERGENT COMPOSITIONS CONTAINING DEXTRINESTERS OF POLY CARBOXYLIC ACIDS BACKGROUND OF THE INVENTION Sequesteringbuilders, particularly polyphosphates, have been used for severaldecades as builder salts in detergent compositions. Phosphate buildersserve multiple purposes, the better known ones of which relate to theircapability for softening water, and, hence protecting the surfactants,particularly the calcium-sensitive surfactants from being, partially orwholly, inactivated by water hardness. Known sequestering builders alsocontribute in a manner which can be termed as synergistic, to cleaningperformance when combined with organic surface-active agents. As anexample, sodium tripolyphosphates are most widely used in granulardetergent compositions, whereas potassium pyrophosphates are preferredfor use in liquid detergent compositions. That latter choice is in orderbecause tripolyphosphates hydrolyze in liquid medium thereby forming acertain amount of orthophosphate which tends to adversely effectcleaning performance.

It has been reported that the presence of phosphates in streams andlakes allegedly contributes to what is called excessive eutrophication.Or, in other words, the presence of said phosphates in water apparentlyfacilitates the uptake by algae and other water plants of nutrientspresent in water, thereby initiating an accelerated growth of said waterplants. This increased growth speed requires more oxygen therebycreating an oxygen deficiency in water which, in turn, results in moredifficult conditions or even impossibility for fish to live in saidwaters. It, therefore, has become desirable to substitute saidpolyphosphate builders, wholly or partially, by effective detergentbuilder salts which do not have the shortcomings of polyphosphates,i.e., which are likely to be eliminated from water, through naturalpurification steps including degradability and biodegradability, undernaturally occurring conditions.

U.S. Pat. No. 2,311,008, Tucker, discloses water-soluble salts ofaliphatic polycarboxylic acids containing, per molecule, three or morecarboxyl groups, as well as ether groupings. These salts canadvantageously be used for water-softening; they can be prepared byetherifying polyhydroxy substances such as starch, glucose, gums and thelike, or polyhydr'ic alcohols such as glycerol, sorbitol, mannitol,xylitol. US. Pat. No. 3,634,392, Lyness, discloses carboxymethylatedderivatives of diand tri-saccharide compounds as detergent builders. Itis known, however, that the prior art carbohydrate derivatives, althoughpossessing detergency characteristics in combination with surface-activeagents, are not well suitable for being used because of their deficientbioegradability characteristics.

It is a main object of this invention to provide detergent compositionswhich are substantially free of phosphorus-containing builder salts.

It is another object of this invention to provide detergentcompositions, capable of effective cleaning performance, containingwater-soluble builder salts which are readily biodegradable and,therefore, will not disturb ecological conditions.

It is still another object of this invention to provide detergentcompositions containing surface-active agents and biodegradablewater-soluble detergent 2 builder salts, namely, low molecular weightcarbohydrates esters.

It is a further object of this invention to provide built detergentcompositions whereby the builder component is degradable andbiodegradable under naturally j occurring conditions, and, accordinglywill not contribute to environmental nuisances.

By utilizing certain detergent builder ingredients, i I

made from low molecular weight carbohydrates and i polycarboxylic acids,in combination with organic sur-' 3 face-active agents, theseabove-described objectives 5 can be attained and built detergentcompositions formulated which are substantially free ofphosphoruscontaining builder salts. Said compositions, especially thedetergent builder component, are biodegradable and thus can be degradedunder naturally occurring conditions, i.e., they do not have, withrespect to ecological conditions, the shortcomings of polyphosphates andthe like detergent builder ingredients known in the art.

SUMMARY OF THE INVENTION I i H OY n wherein n is an integer from about20 to about 120; Y is selected from the group consisting of hydrogen andpolycarboxylic moieties; the degree of substitution 1 (DS) is in therange from about 0.2 to 3; whereby the j weight ratio of said organicsurface active agents to said builders is in the range from about 20:1to about 1: l5.

DETAILED DESCRIPTION OF THE INVENTION Detergent compositions of thisinvention comprise (l) a water-soluble salt of an organic surface-activeagent; and (2) a detergent builder derived from a low molecular weightcarbohydrate esterified with polycarboxylic acids. Each of thesecomponents is discussed in detail hereinafter.

Unless indicated to the contrary, the indications used hereinafter standfor percent by weight.

The instant detergent compositions comprise from about 5% to about 95%,preferably from about 20% to about of a water-soluble organicsurface-active agent selected from the group consisting of anionic,

A. Anionic Soap and Non-Soap Synthetic Detergents This class ofdetergents includes ordinary alkali metal soaps such as the sodium,potassium, ammonium and alkylolammonium salts of higher fatty acidscontaining from about eight to about 24 carbon atoms and preferably fromabout l to about 20 carbon atoms. Suitable fatty acids can be obtainedfrom natural sources such as, for instance, from plant or animal esters(e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil,tallow, whale and fish oils, grease, lard, and mixtures thereof). Thefatty acids also can be synthetically prepared (e.g., by the oxidationof petroleum, or by hydrogenation of carbon monoxide by theFischer-Tropsch process). Resin acids are suitable such as rosin andthose resin acids in tall oil. Napthenic acids are also suitable. Sodiumand potassium soaps can be made by direct saponification of the fats andoils or by the neutralization of the free fatty acids which are preparedin a separate manufacturing process. Particularly useful are the sodiumand potassium salts of the mixtures of fatty acids derived from coconutoil and tallow, i.e., sodium or potassium tallow and coconut soap.

This class of detergents also includes water-soluble salts, particularlythe alkali metal salts of organic sulfuric reaction products having intheir molecular structure an alkyl radical containing from about eightto about 22 carbon atoms and a sulfonic acid or sulfuric acid esterradical. (Included in the term alkyl is the alkyl portion of higher acylradicals.) Examples of this group of synthetic detergents which form apart of the preferred built detergent compositions of the presentinvention are the sodium or potassium alkyl sulfates, especially thoseobtained by sulfating the higher alcohols (C, C carbon atoms) producedby reducing the glycerides of tallow or coconut oil; sodium or potassiumalkyl benzene sulfonates, in which the alkyl group contains from aboutnine to about carbon atoms, in straight chain or branched chainconfiguration, e.g., those of the type described in US. Pat. Nos.2,220,099 and 2,477,383 (especially valuable are linear straight chainalkyl benzene sulfonates in which the average of the alkyl groups isabout 13 carbon atoms abbreviated hereinafter as C,,LAS); sodium alkylglyceryl ether sulfonates, especially those ethers of higher alcoholsderived from tallow and coconut oil; sodium coconut oil fatty acidmonoglyceride sulfonates and sulfates; sodium or potassium salts ofalkyl phenol ethylene oxide ether sulfate with about one to about l0units of ethylene oxide per molecule and in which the alkyl radicalscontain about eight to about 12 carbon atoms.

Anionic phosphate surfactants are also useful in the present invention.These are surface active materials having substantial detergentcapability in which the anionic solubilizing group connectinghydrophobic moieties is an oxyacid of phosphorus. The more commonsolubilizing groups, of course, are SO,H, SO H,

and CO,H. Alkyl phosphate esters such as (RO),.

- P0, and ROPO H, in which R represents an alkyl chain containing fromabout eight to about carbon atoms are useful.

4 These esters can be modified by including in the molecule from one toabout 40 alkylene oxide units, e.g., ethylene oxide units. Formulae forthese modified phosphate anionic detergents are in which R represents analkyl group containing from about eight to 20 carbon atoms, or analkylphenyl group in which the alkyl group contains from about eight to20 carbon atoms, and M represents a soluble cation such as hydrogen,sodium, potassium, ammonium or substituted ammonium; and in which n isan integer from I to about 40.

Another class of suitable anionic organic detergents particularly usefulin this invention includes salts of 2- acyloxy-alkane-lsulfonic acids.These salts have the formula where R is alkyl of about nine to about 23carbon atoms (forming with the two carbon atoms an alkane group); R isalkyl of one to about eight carbon atoms; and M is a salt-formingradical.

The salt-forming radical M in the hereinbefore described structuralformula is a water-solubilizing cation and can be, for example, analkali metal cation (e.g., sodium, potassium, lithium), ammonium orsubstituted-ammonium cation. Specific examples of substituted ammoniumcations include methyl-, dimethyl-, and trimethylammonium cations andquaternary ammonium cations such as tetramethyl-ammonium and dimethylpiperdinium cations and those derived from alkylamines such asethylamine, diethylamine, triethylamine, mixtures thereof, and the like.

Specific examples of beta-acyloxy-alkane-l-sulfon ates, or alternatively2-acyloxy-alkane-l-sulfonates, utilizable herein to provide superiorcleaning levels under substantially neutral washing conditions includethe sodium salt of Z-acetoxy-tridecane-l-sulfonic acid; the potassiumsalt of 2-propionyloxy-tetradecanel -sulfonic acid; the lithium salt of2-butanoyloxy-tetradecane-lsulfonic acid; the sodium salt ofZ-pentanoyloxypentadecane-l-sulfonic acid; the sodium salt of 2-acetoxy-hexadecane-l-sulfonic acid; the potassium salt of2-octanoyloxy-tetradecane-l-sulfonic acid; the sodium salt of2-acetoxy-heptadecane-l-sulfonic acid; the lithium salt ofZ-acetoxy-octadecane-l-sulfonic acid; the potassium salt of2-acetoxy-nonadecane-lsulfonic acid; the sodium salt of2-acetoxy-uncosane-lsulfonic acid; the sodium salt of2-propionyloxy-docd sane-l-sulfonic acid; the isomers thereof.

Preferred beta-acyloxy-alkane-l-sulfonate salts therein are the alkalimetal salts of beta-acetoxyalkanel -sulfonic acids corresponding to theabove for mula wherein R, is an alkyl of about 12 to about 16 carbonatoms, these salts being preferred from the standpoints of theirexcellent cleaning properties and ready where R is a straight chainalkyl group having from six to 20 carbon atoms, R is a lower alkyl grouphaving from one to three carbon atoms, and M is a salt-forming radicalhereinbefore described.

Specific examples of beta-alkyloxy alkane sulfonates or alternatively2-alkyloxy-alkane-l-sulfonates, utilizable herein to provide superiorcleaning and whitening levels under household washing conditionsinclude:

potassium beta-methoxydecanesulfonate,

sodium beta-methoxy-tridecanesulfonate,

potassium beta-ethoxytetradecylsulfonate,

sodium beta-isopropoxyhexadecylsulfonate,

lithium beta-tert-butoxytetradecylsulfonate,

sodium beta-methoxyoctadecylsulfonate, and

ammonium beta-n-propoxydodecylsulfonate.

Additional examples of anionic non-soap synthetic detergents which comewithin the terms of the present invention are the reaction product offatty acids esterified with isethionic acid and neutralized with sodiumhydroxide where, for example, the fatty acids are derived from coconutoil; sodium or potassium salts of fatty acid amide of methyl tauride inwhich the fatty acids, for example, are derived from coconut oil. Otheranionic synthetic detergents of this variety are set forth in US. Nos.2,486,921; 2,486,922; and 2,396,278.

Additional examples of anionic, non-soap, synthetic detergents, whichcome within the terms of the present invention, are the compounds whichcontain two anionic functional groups. These are referred to asdianionic detergents. Suitable di-anionic detergents are thedisulfonates, disulfates, or mixtures thereof which may be representedby the following formulae:

3)z z 4)z z 6 3) 0 2 where R is an acyclic aliphatic hydrocarbyl grouphaving to carbon atoms and M is a water-solubilizing cation, forexample, the C to C disodium 1,2-alkyldisulfates, C to Cdipotassium-l,2-alkyldisulfonates or disulfates, disodium l,9-hexadecyldisulfates, C to C disodium-l,2-alkyldisulfonates, disodium 1,9-stearyldisulfates and 6,l0-octadecyldisulfates.

6 The aliphatic portion of the disulfates or disulfonates is generallysubstantially linear, desirable, among other reasons, because it impartsdesirable biodegradable 1 properties to the detergent compound.

The water-solubilizing cations include the customary 1 cations known inthe detergent art, ie., the alkali metals, and the alkaline earthmetals, as well as other metals in group [1A, [1B, "A, [VA and NE of thePeriodic Table except for Boron. The preferred water-solubiliz-.

ing cations are sodium or potassium. These dianionic detergents are morefully described in Brit. Pat. specification No. l,l5l,392.

Still other anionic synthetic detergents include the class designated assuccinamates. This class includes such surface-active agents as disodiumN-octadecylsulfo succinamate; tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl-sulfo-succinamate; diamyl ester ofsodium sulfosuccinic acid; dioctyl ester of sodium sulfosuccinic acid.

Preferred anionic surface-active agents for use in the compositions ofthe instant invention include alkyl ether sulfates and olefinsulfonates." Said detergents are preferably used in an amount from about20% to about The preferred alkyl ether sulfates have the formula whereinR is alkyl or alkenyl of about l0 to about ,20 carbon atoms, x is l to30, and M is a salt-forming cat- Especially preferred are those alkylether sulfates wherein R has from about 14 to about 18 carbon atoms andwherein x has an average value of about 1 to about 6. Specific examplesof especially preferred species are: sodium coconut alkyl ethyleneglycol ether sulfate; sodium tallow alkyl trioxyethylene ether sulfate;sodium tallow alkyl pentaoxyethylene sulfate; ammonium tetradecylpentaoxyethylene sulfate and ammonium lauryl hexaoxyethylene sulfate.

Especially preferred alkyl ether sulfate components have an average(arithmetic mean) carbon chain length within the range of from about 12to 16 carbon atoms,

preferably from about 14 to 15 carbon atoms; and an average (arithmeticmean) degree of ethoxylation of from about 1 to 4 moles of ethyleneoxide, preferably from about 2 to 3 moles of ethylene oxide.

Such mixtures comprise from about 0.05% to 5% by weight of mixture of Ccompounds, from about 55% to 70% by weight of mixture of C1445compounds, from about 25% to 40% by weight of mixture of C compounds andfrom about 0.1% to 5% by weight of mixture of C1849 compounds. Inaddition, such preferred alkyl ether sulfate mixtures comprise fromabout 15% to 25% by weight of mixture of compounds having a degree ofethoxylation of 0, from about 50% to 65% by weight of mixture ofcompounds having a degree of 5 sawe. 1

gredients can be produced by sulfonation of a-olefrns by means ofuncomplexed sulfurdioxide followed by July 25, 1967, enclosed herein byreference.

' Said a-olefin sulfonates can be represented either by individualspecies or by mixtures containing structurally difierent sulfonationproducts, Preferred mixtures are disclosed by Kessler, et al.; one suchmixture consists essentially of from about 30% to about 70% by weight ofa Component A, from about 20% to about 70% by weight of a Component B,and from about 2% to about 15% of a Component C, wherein a. saidComponent A is a mixture of double-bond positional isomers ofwater-soluble salts of alkene-lsulfonic acids containing from about 20to about 24 carbon atoms, said mixture of positional isomers includingabout 10% to about 25% of an alpha-beta unsaturated isomer, about 30% toabout 70% of a beta-gamma unsaturated isomer, about 5% to about 25% ofgamma-delta unsaturated isomer, and about 5% to about of a delta-epsilonunsaturated isomer;

b. said Component B is a mixture of water-soluble salts ofbifunctionally-substituted sulfur-containing saturated aliphaticcompounds containing from about to about 24 carbon atoms, the functionalunits being hydroxy and sulfonate radicals with the sulfonate radicalalways being on the terminal carbon and the hydroxyl radical beingattached to a carbon atom at least two carbon atoms removed from theterminal carbon atoms, at least 90% of the hydroxy radical substitutionsbeing in 3, 4, and 5 positions; and

c. said Component C is a mixture comprising from about 30-95%water-soluble salts of alkene disulfonates containing from about 20 toabout 24 carbon atoms, and from about 5% to about 70% water-solublesalts of hydroxy disulfonates containing from about 20 to about 24carbon atoms, said alkene disulfonates containing a sulfonic groupattached to a terminal carbon atom and a second sulfonate group attachedto an internal carbon atom not more than about six carbon atoms removedTABLE I MlXTURE CHARACTERISTlC ALKYL ETHER SULFATE MIXTURE Averagecarbon chain 1 11 111 IV Length (No. C Atoms) 14.86 14.68 14.86 14.8812-13 carbon atoms (wt. 4% 1% 1% 3% 14-15 carbon atoms (wt. 55% 65% 65%57% 16-17 carbon atoms (wt. 35% 33% 33% 38% 18-19 carbon atoms (wt. 6%1% 1% 2% Average degree of ethoxylation (No. Moles E0) 1.98 2.25 2.253.0 0 moles ethylene oxide (wt. 15% 21% 22.9% 18% 1-4 moles ethyleneoxide (wt. 63% 59% 65% 55% 5-8 moles ethylene oxide (wt. 21% 17% 12% 22%9+ moles ethylene oxide (wt. 1% 3% 0.1% 5% Salt K Na Na Na The preferredolefm sulfonates utilizable herein have from about 12 to about 24 carbonatoms. Said in- 20 from said terminal carbon atom, the alkene doublebond being distributed between the terminal carbon atom and about theseventh carbon atoms, said hydroxy disulfonates being saturatedaliphatic compounds having a sulfonate radical attached to a terminalcarbon, a second sulfonate group attached to an internal carbon atom notmore than about six carbon atoms removed from said terminal carbon atom,and a hydroxy group attached to a carbon atom which is not more thanabout four carbon atoms removed from the site of attachment of saidsecond sulfonate group.

Especially preferred for use in the instant compositions are 3-, 4-, andS-hydroxy allcyl sulfonates and mixtures thereof. Specific examples ofsaid hydroxy-sulfonates include sodium salts of sodium3-hydroxy-n-decy1- 1 -sulfonate,

sodium 3-hydroxy-n-dodecyl- 1 -su1fonate,

sodium 3-hydroxy-n-tetradecy1- 1 -su1fonate,

sodium 3-hydroxy-n-hexadecy1-1-su1fonate,

sodium 3-hydroxy-n-octadecyll -sulfonate,

sodium 3-hydroxy-n-eicosy1- 1 -sulfonate,

sodium 3-hydroxy-n-docosyl- 1 -su1fonate,

sodium 3-hydroxy-n-tetracosyl- 1 -su1fonate,

sodium 4-hydroxy-n-decy1- l -su1fonate,

sodium 4-hydroxy-n-dodecy1- l -sulfonate,

sodium 4-hydroxy-n-tetradecy1- l -su1fonate,

sodium 4-hydroxy-n-hexadecyl- 1 -sulfonate,

sodium 4-hydroxy-n-o ctadecyl- 1 -su1fonate,

sodium 4-hydroxy-n-eicosy1- 1 -su1fonate,

sodium 4-hydroxy-n-docosyl- 1 -su1fonate,

sodium 4-hydroxy-n-tetracosyl-l-sulfonate,

sodium S-hydroxy-n-d ecyl- 1 -sulfonate,

sodium S-hydroxy-n-dodecyl- 1 -sulfonate,

sodium S-hydroxy-n-tetradecyl- 1 -sulfonate,

sodium 5-hydroxy-n-h exadecyl- 1 -su1fonate sodium5-hydroxy-noctadecyll-sulfonate,

sodium S-hydroxy-n-eicosyl- 1 -su1fonate,

sodium S-hydroxy-n-docosyl-l-sulfonate, and

sodium S-hydroxy-n-tetracosyll -su1fonate.

Among these preferred species the 4-hydroxy substituent is preferred,e.g., for use in combination with 3- hydroxyand/or 5-hydroxy-compounds.This means that in a binary system of the 4-substituent in combinationwith the 3- and 5- substituents or either one of these alone, the4-substituent is present in an amount of at least 50% of the mixture of4 and 3 and/or S-substituents.

B. Nonionic Synthetic Detergents Nonionic synthetic detergents may bebroadly defined as compounds produced by the condensation of alkyleneoxide groups (hydrophilic in nature) with an organic hydrophobiccompound, which may be aliphatic or alkyl aromatic in nature. The lengthof the hydrophilic or polyoxyalkylene radical which is condensed withany particular hydrophobic group can be readily adjusted to yield awater-soluble compound having the desired degree of balance betweenhydrophilic and hydrophobic elements.

For example, a well-known class of nonionic synthetic detergents is madeavailable on the market under the trade name of Pluronic. Thesecompounds are formed by condensing ethylene oxide with a hydrophobicbase formed by the condensation of propylene oxide with propyleneglycol. The hydrophobic portion of the molecule which, of course,exhibits water insolubility, has a molecular weight of from about 1,500to 1,800. The addition of polyoxyethylene radicals to this hydrophobicportion tends to increase the water solubility of the molecule as awhole and the liquid character of the product is retained up to thepoint where polyoxyethylene content is about 50% of the total weight ofthe condensation product.

Other suitable nonionic synthetic detergents include:

1. The polyethylene oxide condensates of alkyl phenols, e.g., thecondensation products of alkyl phenols having an alkyl group containingfrom about six to 12 carbon atoms in either a straight chain or branchedchain configuration, with ethylene oxide, the said ethylene oxide beingpresent in amounts equal to to 25 moles of ethlylene oxide per mole ofalkyl phenol. The alkyl substituent in such compounds may be derivedfrom polymerized propylene, diisobutylene, octene, or nonene, forexample.

2. Those derived from the condensation of ethylene oxide with theproduct'resulting from the reaction of propylene oxide and ethylenediamine. For example, compounds containing from about 40% to about 80%polyoxyethylene by weight and having a molecular weight of from about5,000 to about 11,000 resulting from the reaction of ethylene oxidegroups with a hydrophobic base constituted of the reaction product ofethylene diamine and excess propylene oxide, said base having amolecular weight of the order of 2,500 and 3,000, are satisfactory.

3. The condensation product of aliphatic alcohols having from eight to22 carbon atoms, in either straight chain or branched chainconfiguration, with ethylene oxide, e.g., a coconut alcohol-ethyleneoxide condensate having from 5 to 30 moles of ethylene oxide per mole ofcoconut alcohol, the coconut alcohol fraction having from to 14 carbonatoms.

4. Nonionic detergents include nonyl phenol condensed with either about10 or about 30 moles of ethylene oxide per mole of phenol and thecondensation products of coconut alcohol with an average of either about5.5 or about 15 moles of ethylene oxide per mole of alcohol and thecondensation product of about 15 moles of ethylene oxide with one moleof tridecanol.

Other examples include dodecylphenol condensed with 12 moles of ethyleneoxide per mole of phenol; dinonylphenol condensed with 15 moles ofethylene oxide per mole of phenol; dodecyl mercaptan condensed with 10moles of ethylene oxide per mole of mercaptan; bis-(N-Z-hydroxyethyl)lauramide; nonyl 10 phenol condensed with 20 moles of ethylene oxide permole of nonyl phenol; myristyl alcohol condensed with 10 moles ofethylene oxide per mole of myristyl alcohol; lauramide condensed with 15moles of ethylene, oxide per mole of lauramide; and di-iso-octylphenol;condensed with 15 moles of ethylene oxide.

5. A detergent having the formula R,R R N O@ v (amine oxide detergent)wherein R is an alkyl group? containing from about 10 to about 28 carbonatoms, j from zero to about two hydroxy groups and from zero i to aboutfive ether linkages, there being at least one diethyltetradecylamineoxide, dipropyldodecylamine oxide, bis-(2-hydroxyethyl)dodecylamineoxide, bis- (Z-hydroxyethyl )-3-dodecoxyl -hydroxypropylamine oxide,(2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleylamine oxide,dimethyl-( 2-hydrox ydodecyl)amine oxide, and the corresponding decyl,hexadecyl and octadecyl homologs of the above compounds.

6. A detergent having the formula t l r P (sulfoxide detergent) whereinR, is an alkyl radical containing from about 10 to about 28 carbonatoms, from zero to about five ether linkages and from zero to about twohydroxyl substituents at least one moiety of 3 R being an alkyl radicalcontaining zero ether linkages f and containing from about 10 to about18 carbon. atoms, and wherein R is an alkyl radical containing from oneto three carbon atoms and from one to two 1 hydroxyl groups: octadecylmethyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide,3- hydroxytridecyl methyl sulfoxide, 3-methoxytridecyl i methylsulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, octadecyl2-hydroxyethyl sulfoxide, dodecylethyl sulfoxide. Of all theabove-described types of nonionic surfactants, preferred nonionicsurfactants include the condensation product of nonyl phenol with about9.5 moles of ethylene oxide per mole of nonyl phenol, thecondensationproduct of coconut fatty alcohol with about 6 moles of ethylene oxideper mole of coconut fatty alcohol, the condensation product of tallowfatty alcohol with about l 1 moles of ethylene oxide per mole of tallowfatty alcohol and the condensation product of: a secondary fatty alcoholcontaining about 15 carbon: atoms with about 9 moles of ethylene oxideper mole of fatty alcohol.

C. Ampholytic Synthetic Detergents Ampholytic synthetic detergents canbe broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines, in which thealiphatic radical may be straight chain or branched and wherein one ofthe aliphatic substituents 1 contains from about eight to 18 carbonatoms and at least one contains an anionic water-solubilizing group,e.g., carboxy, sulfo, sulfato. Examples of compounds falling within thisdefinition are sodium 3- (dodecylamino)-propionate, sodium 3-(dodecylamino)propanel -sulfonate, sodium 2- (dodecylamino)ethylsulfate, sodium 2-(dime- D. Zwitterionic Synthetic DetergentsZwitterionic synthetic detergents can be broadly described asderivatives of aliphatic quaternary ammonium and phosphonium or tertiarysulfonium compounds, in which the cationic atom may be part of aheterocyclic ring, and in which the aliphatic radical may be straightchain or branched, and wherein one of the aliphatic substituentscontains from about three to 18 carbon atoms, and at least one aliphaticsubstituent contains an anionic water-solubilizing group, e.g., carboxy,sulfo, sulfato, phosphato, or phosphono. Examples of compounds fallingwithin this definition are 3-(N,N-dimethyl-N-hexadecyl-ammonio)-2-hydroxypropane- 1 -sulfonate, 3-( N,N-dimethyl-N-hexadecylammonio )-prop ane- 1 -sulfonat'e,2-(N,N-dimethy1-N- dodecylammonio)acetate, 3-(N,N-dimethyl N-dodecylammonio)propionate, 2-(N,N-dimethyl-N- octadecylammonio)-ethylsulfate, Z-(trimethylammonio)ethyl dodecylphosphonate, ethyl 3-(N,N-dimethyl-N-dodecylammonio)-propylphosphonate, 3-(P,P-dimethyl-P-dodecylphosphonio)-propane- 1 -sulfonate,2-(S-methyl-S-tert.hexadecyl-sulfonio)ethanel-sulfonate,3-(S-methyl-S-dodecylsulfonio)propionate, sodium2-(N,N-dimethyl-N-dodecylammonio)e- ,thylphosphonate,4-(S-methyl-S-tetradecylsulfonio)butyrate, l2-hydroxyethy1)-2-undecylimidazoliuml-acetate,2-(trimethylammonio)octadecanoate, and

, 3-( N,N-bis-( 2-hydroxyethyl )-N-octadecylammonio)-2-hydroxypropane-l-sulfonate. Some of these detergents are described inthe following U.S. Patents: U.S. Pat. Nos. 2,129,264; 2,178,353;2,774,786; 2,813,898; and 2,828,332.

Of all the above-described types of zwitterionic surfactants, preferredcompounds include 3(N,N-dimethyl-N-alkylammonio)-propane-l-sulfonate and3(N,N- dirnethyl-N-alkylammonio )-2-hydroxypropanel -sulfonate whereinin both compounds the alkyl group averages 14.8 carbon atoms in length;3(N,N-dimethyl-N- hexadecylammonio)-propane-l-sulfonate; 3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-lsulfonate;3-(N-dodecylbenzyl-N,N-dimethylamrnonio)-propane- 1 -su1fonate;(N-dodecylbenzyl-N,N-dimethylammonio)acetate;3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate;6-(N-dodecy1benzyl-N,N-

dirnethylammonio)hexanoate; and (N,N-dimethyl-N- 3hexadecylammonio)acetate.

Another essential ingredient for use in the instant compositions m awater-soluble biodegradable detergent builder salt. Said builder has thegeneral formula:

cmov

H (Iro H 1 H \l c wherein n is an integer from about 20 to about Y isselected from the group consisting of hydrogen and polycarboxylic acids;the degree of substitution is in the range from about 0.2 to 3. Theweight ratio of said builders to the organic surface-actives, as alreadyreferred to hereinbefore, is in the range from about 15:1 to about 1:20,preferably from 8:1 to 1:12. The builder is used in an amount from about5% to about 95%, preferably from about 20% to about 70%.

The essential builder component is an ester of polysaccharides andpolycarboxylic acids.

The polysaccharides suitable for use have a degree of polymerization ofabout 20 to about 120, preferably of about 20 to about 80, and iscommonly known as dextrin. Dextrins are derived from more highlypolymerized branched and linear polysaccharides such as starch andglycogen. These raw materials are hydrolyzed to dextrin thereby usingany technique suitable for that purpose.

By way of example, dextrin can be produced from dryroasted starch byvarious degradation-recombinations. The species known as white dextrinis, for example, prepared by hydrolytic breakdown of starch in thepresence of moisture and high acidity at a temperature of about C.Yellow dextrin is prepared from starch at temperatures from about 150 to200C under conditions of moderate acidity and low moisture (as comparedto the conditions for preparing white dextrins). Species prepared bymolecular rearrangement and repolymerization are, also, well-known andmay serve as raw material for the essential builder ingredient.

Starch and glycogen are the commonest food reserve materials of theplant animal kingdom, respectively. Starch is a mixture of two mainpolysaccharide components, namely, a linear species called amylose and ahighly branched species called amylopectin. Glycogen is constituted of asingle polysaccharide species with a similar, but more highly branchedstructure than amylopectin.

In general, starches contain, depending upon their origin, up to 30% ofamylose and up to 98% of amylopectin.

Amylose contains linear chains of l 4' a-D- glycopyranose having adegree of polymerization of about 1,000 to about 6,000. Amylopectin hasa molecular weight in the range from 10 to 10 million. It has a branchedstructure whereby the chains having 1 4 a- D-glycopyranose bonds arebranched through 1 6 linkages. Glycogen is essentially similar toamylopectin except that the degree of branching is somewhat greater. Formore details, see POLYSACCHARIDES, by Gerald O. Aspinall, PergarnmonPress, New York, 1st Edition, 1970, incorporated herein by reference.

Polycarboxylic acids suitable for the dextrin esterification includearomatic and aliphatic polycarboxylic acids. Examples of preferredaromatic species include mellitic acid, benzene pentacarboxylic acid,benzene wherein R is selected from:

Cl-l COOH; CH CH COOH;

cloon (icon coon coon and R is selected from:

CH COOH; CH CH COOH;

cn -cn, coon coon coon coon coon: coon; c =c coon coon and CH CH wherebyR and R form a closed ring structure in the event said radicals areselected from:

CIOOH (ITOOH COOH COOH Specific examples of polyethercarboxylic acidsinclude oxydiacetic acid having the formula:

/ CH ,COOH

oxydisuccinic acid having the formula:

coon coon cn cn, cn cn,

coon coon carboxy methyl oxysuccinic acid having the formula:

coon coon cn-cn, cn,-coon furan tetracarboxylic acid having the formula:

and tetrahydrofuran tetracarboxylic acid having the formula:

coon poon C OOH COOH The degree of substitution (with respect to thehydroxyl functions of the dextrin) is in the range from ents of theinstant compositions at normal usage concentration, for example, inlaundry solutions containing from about 0.05% to about 1% of detergentcompositions of the instant invention. The biodegradable builders foruse in the instant compositions can be prepared using techniques knownin the art. As an example, dextrin succinate was prepared as describedhereinafter.

PREPARATION OF DEXTRIN SUCCINATE Dextrin (50.0 g., 0.3 mole) was placedin a 2-liter, three-necked flask along with 1 liter of pyridine. Theflask was equipped with a magnetic stirrer, Dean-Stark trap,thermometer, and an argon inlet.

The above mixture was refluxed for 1 hour while -l00 ml. of distillatewas collected (this removes excess moisture). The reactants were thencooled to 60-70C and succinic anhydride (120 g., 12 moles) was added allat once. The reaction mixture was then heated at C overnight.

Most of the pyridine was then stripped from the dextrin reactionmixture; thereafter the residue was cooled in an ice bath and acidifiedto pH 2-3 with hydrochloric acid. A sticky mass fon'ned which was hardto stir.

The supernatant was decanted and the residue was washed three times withwater. The residue was dissolved in acetone and ether was added until athick, molasses-like solid precipitated. The supernatant was decantedand the remaining solvent was removed on a flash evaporator. This wasrepeated until a crystalline product was obtained. The product was thenvacuum dried to give 81 g. of dextrin succinate.

The protonated succinates can be converted to the TABLE II AverageDegree of Polymerization Polycarboxylic Average Degree of of Dextrin (n)Acid Moiety Substitution (DS) 50 Succinic acid 2.0 30 Maleic acid 2.0

TABLE lI-continued Average Degree of Polymerization Average Degree ofPolycarboxylic carboxylic acid The preferred builder ingredients listedabove have a degree of esterification (DE) of about 1, i.e., one of theesterifiable carboxylic moieties per mole of polyacid reacts, on theaverage, with one hydroxyl group of the dextrin.

The free (non-esterified) carboxylic radicals can be neutralizedpartially or wholly whereby the choice of the neutralizing cation, to acertain extent, determines the water solubility. Suitable cations can berepresented by sodium, potassium, lithium, amines and alka- .nolaminessuch as triethanolamine, diethanolamine and monoethanolamine.

1n the foregoing, the essential ingredients which are comprised in thedetergent formulations of this invention are described in great detail.However, in the finished detergent formulations of this invention, thereare usually added other optional detergent composition ingredients whichmake the product more effective and more attractive. So, for example,organic and inorganic peroxy bleach compounds can be incorporated inthese compositions in an amount from about 5% to about 40%.

.'lhe peroxy bleach compound can be represented by all usual inorganicand organic ingredients which are known to be satisfactory for beingincorporated for that purpose in detergent compositions. Examples ofinorganic peroxy bleach compounds are the alkaline metal salts ofperborates, percarbonates, persilicates, persulfates, and perphosphates.As is well known, the perborates can have different degrees ofhydration. Although frequently the tetrahydrate form is used, it is forcertain purposes desirable to incorporate the perborates having a lowerdegree of hydration water, for example, 1 mole, 2 moles, or 3 moles.Organic peroxy bleach agents may be used as well. The like ingredientscan be incorporated as such, i.e., they have been prepared previously orthey may be prepared in situ through the addition of, for example, anyperoxy bleach agents suitable for being used in combination with anorganic peroxy-bleach activator.

Specific examples of the organic peroxy-bleach compounds are thewater-soluble salts of monoand diperoxy acids such as perazelaic acid,monoperoxyphthalic acid, diperoxy-terephthalic acid, 4-chlorodiperoxyphthalic acid. Preferred aromatic peracids include thewater-soluble salts of diperisophthalic acid, m-chloroperbenzoic acidand p-nitroperbenzoic acid.

In the event the peroxy bleach compound is to be prepared in situ, thenits precursors, i.e., the peroxy bleach agent and peroxygen activatorsare to be added separately to the detergent composition. The peroxygenbleach can be represented by all oxyen bleaching agents which arecommonly used in detergent technology, i.e., organic and inorganicspecies, as mentioned hereinbefore. The activating agents can berepresented by all the oxygen activators known as being suitable for usein detergent technology. Specific examples of the preferred activatorsinclude acylated glycoluriles, tetra-acetyl methylene diamine,tetra-acetyl ethylene diamine, triacetyl isocyanurate andbenzoylimidazole. Acid anhydride activators which bear at least onedouble bond between carbon atoms in 01,01 to the carbonyl group of theanhydride radical can be used as well. Examples thereof are phthalic andmaleic anhydrides. Especially preferred bleach activators are based onaldehydes, ketones, and bisulfite adducts of aldehydes and ketones.Examples of these esp; cially preferred activators include:1,4-cyclohexanedione; cyclohexanone; 3-oxo-cyclohexylacetic acid;4-tertbutylcyclohexaneone; 5-diethylmethylammonio-Z-pentanone nitrate;N- methyLmorpholinioacetophenone nitrate; acetone, methyl ethyl ketone;3-pentanone; methyl-pyruvate; N-methyl-4-oxo-piperidine oxide;l,4-bis(N-methyl-4- oxopiperidiniomethyl) benzene chloride;N-methyltropinonium nitrate; thiapyranonium nitrate; N-benzyl;N-methyl-4-oxopiperidinium nitrate; N ,N-dimethyl-4-oxo-piperidiniumnitrate; di-Z-pyridyl ketone; and chloral hydrate.

In the event the peracid is prepared in situ, then the molar ratio ofperoxygen bleach agent to bleach activator shall preferably be in therange from about 5:1 to 1:2, especially from 2:1 to 1:12.

Other detergent composition ingredients used herein include sudsregulating agents such as suds boosters and suds suppressing agents,tarnish inhibitors, soil suspending agents, buffering agents, enzymes,brighteners, flurorescers, perfumes, dyes and mixture. The suds boosterscan, e.g., be represented by diethanolamides. Silicones, hydrogenatedfatty acid, and hydrophobic alkylene oxide condensates can be used inthe like compositions for suds suppressing purposes or, more generally,for suds regulating purposes. Benzotn'azole and ethylenethiourea can beused as tarnish inhibitors. Carboxymethyl cellulose is a well-known soilsuspensing agent. The above additional ingredients, when used in theinstant compositions, shall be employed in the usual ranges. Enzymes arefrequently added because of their contribution to degrade soil therebyrendering said soil more soluble and more easily removable which, inturn, amounts to a cleaning perfonnance improvement. Because of theirspecific soil degrading action, mixtures of different enzyme species arefrequently preferred. Especially preferred for use in the instantcompositions is an enzyme selected from the group consisting ofproteases, amylases, lipases and peroxidases mixtures thereof. Saidenzymes are used in an amount from 0.001% to 3.00% of the detergentcomposition.

The detergent compositions of the instant invention can be of anyphysical state, i.e., liquid, pasty, powdered and granular. Highlypreferred are solid, including powdered and granular, detergentcompositions.

The following examples are illustrative but do not limit the novelcompositions of the present invention.

l-methyl-4-oxo-tetrahydro- EXAMPLE I Detergent compositions having thefollowing formula provided comparable cleaning performance when used incomparative cleaning tests.

Composition A Example I Sodium dextrin succinate (average degree ofpolyl merization (n) about 50) OS 2.2 6 parts Sodium tripolyphosphate 6pans Sodium B-acetoxyhexadecyl sulfonate 4 parts Sodium linear C alkylbenzene sulfonate 4 parts DS degree of substitution Substantiallyidentical results are obtained in the event the sodium dextrin succinateis replaced with an equivalent amount of the water-soluble salts of anyof the dextrin polycarboxylates listed in Table II hereinbefore.

The detergent compositions of Example I, especially the polycarboxylateddextrin builders, are substantially biodegradable. In contrast thereto,detergent compositions containing polycarboxylated corn starch buildersare substantially non-biodegradable upon testing under identicalconditions.

EXAMPLE II An effective and readily biodegradable detergent compositionhas the following formula:

Sodium tallow alkyl trioxyethylene sulfate 35 parts Sodium dextrin (naverages 60) oxydisuccinate (DS L8) parts Sodium sulfate 28 parts Minoringredients including moisture, brightener, dyes, 40

perfumes Balance to 100 parts LII EXAMPLE "I The following compositionprovides excellent cleaning and is biodegradable.

Sodium salt of sulfonated l-hexadecene 25 parts Sodium dextrin (naverages 40) succinate (DS 1.3) 20 parts Sodium sulfate 20 parts Sodiumperborate 30 parts Substantially similar results are obtained in theevent the sodium salt of sulfonated l-hexadecene is substituted by anequivalent amount of a surface-active mixture, said mixture consistingessentially of about 50% of a Component A, about 40% of a Component B,and about 10% of a Component C, wherein a. said Component A is a mixtureof double-bond positional isomers of water-soluble salts of alkene-1-sulfonic acids containing from about 20 to about 24 carbon atoms, saidmixture of positional isomers 5 including about 20% of an alpha-betaunsaturated f isomer, about 50% of a beta-gamma unsaturated j isomer,about 20% of gamma-delta unsaturated isomer, and about 10% of adelta-epsilon unsatu rated isomer; b. said Component B is a mixture ofwater-soluble positions; and

said Component C is a mixture comprising from about water-soluble saltsof alkene disulfonates containing from about 20 to about 24 carbonatoms, and from about 30% water-soluble salts of hydroxy disulfonatescontaining from about 20 to j about 24 carbon atoms, said alkenedisulfonates containing a sulfonic group attached to a terminal carbonatom and a second sulfonate group attached to an internal carbon atomnot more than about six carbon atoms removed from said terminal carbonatom, the alkene double bond being distributed between the terminalcarbon atom and about 5 the seventh carbon atoms, said hydroxydisulfonates being saturated aliphatic compounds having a sulfonateradical attached to a terminal carbon, a

second sulfonate group attached to an internal carbon atom not more thanabout six carbon atoms removed from said terminal carbon atom, and ahydroxy group attached to a carbon atom which is not more than aboutfour carbon atoms removed from the site of attachment of said secondsulfonate group.

Substantially similar results are also obtained when the sodium salt ofsulfonated l-hexadecene is replaced with an equivalent amount of amixture of the sodium salts of 3-, 4-, and S-hydroxy alkyl sulfonates,whereby in a binary system of these, the 4-hydroxy is present in excessof 50% by reference to the sum of the 3-, or 5- hydroxy with the4-hydroxy alkyl sulfonates.

EXAMPLE lV Another detergent composition of this invention which isreadily biodegradable and provides excellent cleansing has the followingformula:

Sodium salt of sulfonated 40 parts Substantially similar results arealso obtained in the event the sodium perborate tetrahydrate issubstituted 19 by an equivalent amount of perazelaic acid,monoperoxy-phthalic acid, diperoxy-terephthalic acid, 4chlorodiperoxy-phthalic acid.

What is claimed is: l. A detergent composition, consisting essentiallyof a. from about to about 95% by weight of a watersoluble organicsurface-active agent selected from the group consisting of anionic,nonionic, ampholytic and zwitterionic detergents and mixtures thereof;and b. from about 95% to about 5% by weight of a watersoluble builderconsisting of dextrin esterified with a polycarboxylic acid selectedfrom mellitic acid, benzene pentacarboxylic acid, benzenetetracarboxylic acid, benzene tn'carboxylic acid, oxydisuccinic acid,carboxymethyloxysuccinic acid, furan tetracarboxylic acid, andtetrahydrofuran tetracarboxylic acid, said builder being characterizedby a degree of substitution from about 0.2 to 3 and a degree ofesterification of l; the weight ratio of the surface-active agent to thebuilder being in the range from about :1 to about 1:15.

2. A detergent composition in accordance with claim 1 wherein thecomponent (a) organic surface-active agent is used in an amount fromabout 20% to about 5 70% by weight.

; 3. A detergent composition in accordance with claim 2 wherein thecomponent (b) builder salt is used in an amount from about 20% to about70% by weight.

4. A detergent composition in accordance with claim 3 wherein thebuilder salt has a degree of substitution from about 0.8 to about 2.2.

S. A detergent composition in accordance with claim 1 4 which, inaddition, contains from about 5% to about 40% by weight of a peroxybleach compound.

6. A detergent composition in accordance with claim 5 wherein the peroxybleach compound is a water-soluble salt selected from the groupconsisting of perazelaic acid, monoperoxy-phthalic acid,diperoxy-terephthalic acid, 4-chlorodiperoxyphthalic acid,diperisophthalic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid,

. and mixtures thereof.

7. A detergent composition in accordance with claim 6 wherein the peroxybleach compound is prepared in i situ and whereby the precursors forsaid peroxy bleach compounds consist of an inorganic compound selected 1from the alkaline metal salts of perborates, percarbonj ates,persilicates, persulfates, perphosphates, and mixtures thereof; and aperoxygen bleach activator selected from the group consisting ofacylated glycoluriles, tetra-acetyl methylene diamine, tetra-acetylethylene diamine, triacetyl isocyanurate, benzoylimidazole, maleicanhydride, phthalic anhydride,

" 1,4-cyclohexanedione; cyclohexanone; 3-oxo cyclohexylacetic acid;4-tertbutylcyclohexanone; 5-

; diethylmethylammonio-Z-pentanone nitrate;4-methylmorpholinioacetophenone nitrate; acetone; methyl ethyl ketone;3-pentanone; methyl pyruvate; N-methyl- 4-oxo-piperidone oxide; l,4-bis(N-methyl-4- f oxopiperidiniomethyl) benzene chloride; N-methyl- 20tropinonium nitrate; l-methyl-4-oxotetrahydrothiapyranonium nitrate;N-benzyl; N-methyl-4- oxopiperidinium nitrate;N,N-dimethyl-4-oxopiperidinium nitate; di-2-pyridyl ketone; chloralhydrate and mixtures thereof; the molar ratio of peroxygen bleach agentto bleach activator being in the range of from about 5:1 to about 1:2.

8. A detergent composition in accordance with claim 3 wherein the weightratio of the component (a) organic surfaceactive agent to component (b)detergent builder is in the range from 12:1 to 1:8.

9. A detergent composition in accordance with claim 8 wherein theorganic surface-active agent is selected from the group consisting of i.olefin sulfonates having from about 12 to about 24 carbon atoms; and ii.alkylethersulfates having the general formula wherein R is alkyl oralkenyl of about 10 to about 20 carbon atoms, x is 1 to 30 and M is asalt-fonning cat- I011.

10. A detergent composition in accordance with claim 9 wherein the alkylether sulfate organic surfaceactive agent is selected from the groupconsisting of sodium coconut alkyl ethylene glycol ether sulfate;lithium tallow alkyl glycol ether sulfate; sodium tallow alkylpentaoxyethylene sulfate; ammonium tetradecylpentaoxy ethylene sulfate;ammonium lauryl hexaoxyethylene sulfate; sodium tallow alkyltrioxyethylene sulfate; and alkyl ether sulfate mixture having anaverage carbon chain length of from about 14 to 15 carbon atoms and anaverage degree of ethoxylation between about 2 and 3 moles of ethyleneoxide, said alkyl ether sulfate mixture comprising from about 0.05% to5% by weight of said alkyl ether sulfate mixture of compounds containing12 to 13 carbon atoms;

from about 55% to by weight of said alkyl ether sulfate mixture ofcompounds containing 14 to 15 carbon atoms;

from about 25% to 40% by weight of said alkyl ether sulfate mixture ofcompounds containing 16 or 17 carbon atoms;

from about 0.1% to 5% by weight of said alkyl ether sulfate mixture ofcompounds containing 18 or 19 carbon atoms;

from about 15% to 25% by weight of said alkyl ether sulfate mixture ofcompounds having a degree of ethoxylation of zero; from about 50% to 65%by weight of said alkyl ether sulfate mixture of compounds having adegree of ethoxylation of from 1 to 4;

from about 12% to 22% by weight of said alkyl ether sulfate mixture ofcompounds having a degree of ethoxylation of from 5 to 8; and

from about 0.5% to 10% by weight of said alkyl ether sulfate mixture ofcompounds having a degree of ethoxylation greater than 8; and mixturesthereof.

1. A DETERGENT COMPOSITION, CONSISTING ESSENTIALLY OF A. FROM ABOUT 5%TO ABOUT 95% BY WEIGHT OF A WATER-SOLUBLE ORGANIC SURFACE-ACTIVE AGENTSELECTED FROM THE GROUP CONSISTING OF ANIONIC, NONIONIC, AMPHOLYTIC ANDZWITTERIONIC DETERGENTS AND MIXTURES THEREOF, AND B. FROM ABOUT 95% TOABOUT 5% BY WEIGHT OF A WATER-SOLUBLE BUILDER CONSISTING OF DEXTRINESTERIFIED WITH A POLYCARBOXYLIC ACID SELECTED FROM MELLITIC ACID,BENZENE PENTACARBOXYLIC ACID, BENZENE TETRACARBOXYLIC ACID, BENZENETRICARBOXYLIC ACID, OXYDISUCCINIC ACID, CARBOXYMETHYLOXYSUCCINIC ACID,FURAN TETRACARBOXYLIC ACID, AND TETRAHYDROFURAN TETRACARBOXYLIC ACID,SAID BUILDER BEING CHARACTERIZED BY A DEGREE OF SUBSTITUTION FROM ABOUT0.2 TO 3 AND A DEGREE OF ESTERIFICATION OF 1, THE WEIGHT RATIO OF THESURFACE-ACTIVE AGENT TO THE BUILDER BEING IN THE RANGE FROM ABOUT 20:1TO ABOUT 1:15.
 2. A detergent composition in accordance with claim 1wherein the component (a) organic surface-active agent is used in anamount from about 20% to about 70% by weight.
 3. A detergent compositionin accordance with claim 2 wherein the component (b) builder salt isused in an amount from about 20% to about 70% by weight.
 4. A detergentcomposition in accordance with claim 3 wherein the builder salt has adegree of substitution from about 0.8 to about 2.2.
 5. A detergentcomposition in accordance with claim 4 which, in addition, contains fromabout 5% to about 40% by weight of a peroxy bleach compound.
 6. Adetergent composition in accordance with claim 5 wherein the peroxybleach compound is a water-soluble salt selected from the groupconsisting of perazelaic acid, monoperoxy-phthalic acid,diperoxy-terephthalic acid, 4-chlorodiperoxyphthalic acid,diperisophthalic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid,and mixtures thereof.
 7. A detergent composition in accordance withclaim 6 wherein the peroxy bleach compound is prepared in situ andwhereby the precursors for said peroxy bleach compounds consist of aninorganic compound selected from the alkaline metal salts of perborates,percarbonates, persilicates, persulfates, perphosphates, and mixturesthereof; and a peroxygen bleach activator selected from the groupconsisting of acylated glycoluriles, tetra-acetyl methylene diamine,tetra-acetyl ethylene diamine, triacetyl isocyanurate, benzoylimidazole,maleic anhydride, phthalic anhydride, 1,4-cyclohexanedione;cyclohexanone; 3-oxo-cyclohexylacetic acid; 4-tertbutylcyclohexanone;5-diethylmethylammonio-2-pentanone nitrate;4-methylmorpholinioacetophenone nitrate; acetone; methyl ethyl ketone;3-pentanone; methyl pyruvate; N-methyl-4-oxo-piperidone oxide;1,4-bis(N-methyl-4-oxopiperidiniomethyl) benzene chloride;N-methyltropinonium nitrate; 1-methyl-4-oxotetrahydrothiapyranoniumnitrate; N-benzyl; N-methyl-4-oxopiperidinium nitrate;N,N-dimethyl-4-oxo-piperidinium nitate; di-2-pyridyl ketone; chloralhydrate and mixtures thereof; the molar ratio of peroxygen bleach agentto bleach activator being in the range of from about 5:1 to about 1:2.8. A detergent composition in accordance with claim 3 wherein the weightratio of the component (a) organic surfaceactive agent to component (b)detergent builder is in the range from 12:1 to 1:8.
 9. A detergentcomposition in accordance with claim 8 wherein the organicsurface-active agent is selected from the group consisting of i. olefinsulfonates having from about 12 to about 24 carbon atoms; and ii.alkylethersulfates having the general formula RO(C2H4O)xSO3M wherein Ris alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30and M is a salt-forming cation.
 10. A detergent composition inaccordance with claim 9 wherein the alkyl ether sulfate organicsurface-active agent is selected from the group consisting of sodiumcoconut alkyl ethylene glycol ether sulfate; lithium tallow alkyl glycolether sulfate; sodium tallow alkyl pentaoxyethylene sulfate; ammoniumtetradecylpentaoxy ethylene sulfate; ammonium lauryl hexaoxyethylenesulfate; sodium tallow alkyl trioxyethylene sulfate; and alkyl ethersulfate mixture having an average carbon chain length of from about 14to 15 carbon atoms and an average degree of ethoxylation between about 2and 3 moles of ethylene oxide, said alkyl ether sulfate mixturecomprising from about 0.05% to 5% by weight of said alkyl ether sulfatemixture of compounds containing 12 to 13 carbon atoms; from about 55% to70% by weight of said alkyl ether sulfate mixture of compoundscontaining 14 to 15 carbon atoms; from about 25% to 40% by weight ofsaid alkyl ether sulfate mixture of compounds containing 16 or 17 carbonatoms; from about 0.1% to 5% by weight of said alkyl ether sulfatemixture of compounds containing 18 or 19 carbon atoms; from about 15% to25% by weight of said alkyl ether sulfate mixture of compounds having adegree of ethoxylation of zero; from about 50% to 65% by weight of saidalkyl ether sulfate mixture of compounds having a degree of ethoxylationof from 1 to 4; from about 12% to 22% by weight of said alkyl ethersulfate mixture of compounds having a degree of ethoxylation of from 5to 8; and from about 0.5% to 10% by weight of said alkyl ether sulfatemixture of compounds having a degree of ethoxylation greater than 8; andmixtures thereof.